US3476708A - Hydrazine-modified polyester resins useful in insulating lacquers for wires - Google Patents

Hydrazine-modified polyester resins useful in insulating lacquers for wires Download PDF

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Publication number
US3476708A
US3476708A US676023A US3476708DA US3476708A US 3476708 A US3476708 A US 3476708A US 676023 A US676023 A US 676023A US 3476708D A US3476708D A US 3476708DA US 3476708 A US3476708 A US 3476708A
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US
United States
Prior art keywords
hydrazine
wire
weight
modified polyester
lacquers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US676023A
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English (en)
Inventor
Gerhard Schade
Franz Blaschke
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Dynamit Nobel AG
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Dynamit Nobel AG
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]

Definitions

  • This invention relates to insulating lacquers or varnishes for wires. More particularly, it relates to modified polyester resins of terephthalic and/or isophthalic acid with diand polyhydric alcohols, to wire insulating varnishes or lacquers made therefrom and to a process for preparing the same.
  • polyester resins produced with the use of proportions of various polyfunctional compounds, such as dicarboxylic acids containing imide groups from trimellitic acid anhydride and aromatic diamines or aminocarboxylic acids; hydroxycarboxylic acids containing imide groups from trimellitic acid anhydride and alkanolamines; certain silanes and siloxanes, tris(hydroxyethyl) isocyanurate; aliphatic diamines, aminocarboxylic acids, or lactams; tris(hydroxymethyl)-aminomethane, etc.
  • polyfunctional compounds such as dicarboxylic acids containing imide groups from trimellitic acid anhydride and aromatic diamines or aminocarboxylic acids; hydroxycarboxylic acids containing imide groups from trimellitic acid anhydride and alkanolamines; certain silanes and siloxanes, tris(hydroxyethyl) isocyanurate; aliphatic diamines, aminocarboxylic acids, or lactams; tris
  • one of the objects of the present invention is to provide wire insulating lacquers or varnishes having advantageous properties and which overcome the deficiencies of the prior art compositions.
  • Another object of the present invention is to provide ice a process for preparing lacquers for insulating wires which may be carried out in an efficacious and economical manner.
  • a further object of the invention is to provide wire insulating lacquers of high quality.
  • a still further object of the invention is to provide wire insulating lacquers which have an improved abrasion resistance, heat or high temperature shock resistance, and curing and processing speed as well as wire insulations produced therewith which have a resistance to pressure at high temperatures.
  • Yet another object of the invention is to provide a modified polyester resin having useful properties.
  • wire insulating lacquers containing polyester resins can be improved with respect to the abovementioned properties by incorporating hydrazine hydrate, or aqueous solutions thereof, into the polyester-based lacquers.
  • These lacquers are produced by concomitantly employing the hydrazine hydrate, or aqueous solutions thereof, during the manufacture of the polyester resins, thereby incorporating hydrazine into the polyester chain by condensation.
  • the present invention relates to modified polyester resins and to wire lacquers or varnishes made therefrom, comprising modified polyester resins of terephthalic acid, isophthalic acid, or mixtures thereof, with glycols, as well as more than dihydric (polyhydric) alcohols, and conventional solvents, hardeners and, if desired, further additives, wherein the polyester resins contained in these lacquers have hydrazine condensed therein.
  • the nitrogen content of the polycondensates of this invention is in the range of 0.5 to by weight, preferably 2 to 6% by weight.
  • the curing process takes place in the manner customarily used with the conventional polyester resins by way of the predominantly chain-positioned hydroxyl groups by means of conventional curing agents, such as alkyl and aryl titanates, polyisocyanate cleaving agents and metal salts of organic acids.
  • conventional curing agents such as alkyl and aryl titanates, polyisocyanate cleaving agents and metal salts of organic acids.
  • the resins contained in the wire insulating lacquers having the composition of the present invention are obtained in a particularly simple and economical manner by first esterifying terephthalic acid or isophthalic acid, or mixtures thereof, with a mixture of a glycol and a polyhydric alcohol or by transesterifying lower alkyl esters of the above-mentioned acids with the polyalcohol mixture. Then, the hydrazine hydrate, or an aqueous solution therof, preferably an approximately 80% by weight solution, is added thereto. The mixture is then refluxed for at least about 3 hours, and the water is therafter distilled off. The mixture is then maintained at a temperature of approximately 230 to 265 C.
  • the processing speed was varied. Only the results of the most favorable processing speed in each case are shown.
  • the test for abrasion resistance was conducted according to NEMA/MW 55-1955 (number of double strokes at a load of 405 grams).
  • the coil turn test was made at a pretensioning (preliminary elongation), 1000 g. load and a coiling speed of 280 rpm. The results shown indicate at what diameter of the mandrel (expressed as one bare-wire diameter or a multiple thereof) that there was not yet any damage to the layer of lacquer.
  • the heat shock resistance was determined by producing coiled turns with one mandrel diameter, at a load of g. with 280 rpm, and subjecting these turns for 15 minutes to various temperatures. The boundary or threshold temperature at which there was barely no damage as yet to the lacquer film is indicated.
  • the resistance to pressure under heat was determined according to DIN (German Industrial Standard) 46, 45 3, Draft of April 1965, at a load of 800 grams.
  • a wire lacquer was prepared with the resultant polyester resin using the following formulation:
  • EXAMPLE 1 The resin described in the above comparative example (400 parts by weight) was melted at 150 C. Gradually added dropwise thereto was 25 parts by weight of an 80% hydrazine hydrate solution. The reaction mixture was then refluxed for three hours. Thereafter, water, at first, and then glycol were distilled off until a product temperature of 250 C. was reached. After four hours at 250 C., the resin had a viscosity number of 0.15, an acid number of 17, a saponification number of 446, an hydroxyl number of and a nitrogen content of 2.9%.
  • a lacquer was prepared in accordance with the same formulation shown in the comparative example hereinabove.
  • EXAMPLE II Within eight hours, 445 parts by weight of dimethyl terephthalate, 119.6 parts by weight of glycerin, 87 parts by weight of ethylene glycol, 0.1 part by weight of lead octoate and 0.4 part by weight of tetrabutyl titanate were transesterified at 145-220 C. After cooling to 165 C., 26 parts by weight of an 80% hydrazine hydrate solution was added thereto dropwise, and the reaction mixture was refluxed for three hours. Then, the same procedure was followed as described in Example I. The viscosity number of the resultant modified polyester resin was 0.150 and the nitrogen content thereof was 2.4%.
  • a lacquer was prepared with this modified polyester resin with the same formulation as described in the Comparative Example.
  • Abrasion resistance 100 Coil turns 1 High temperature aging 1 Heat shock resistance 220 C. High-temperature pressure resistance 270 C.
  • the resultant modified polyester resin had a viscosity value of 0.162 and a nitrogen content of 4.33%.
  • a lacquered wire was prepared. It showed the following characteristics:
  • Heat shock resistance 240 C High-temperature pressure resistance 270 C.
  • lacquer formulations could be shown, but these are considered to be redundant as lacquer formulation per se is well known in the art.
  • Solvents which may be employed include, for example, aro matic hydrocarbons such as the cresols, xylene, aromatic hydrocarbon cuts from petroleum (such as solvent naphtha) and the like.
  • aro matic hydrocarbons such as the cresols, xylene, aromatic hydrocarbon cuts from petroleum (such as solvent naphtha) and the like.
  • the curing agent or other additives as desired, since these are conventional and any of those conventionally employed may be used in the present invention.
  • the amount of hydrazine to be added to the polyesters during the preparation of the modified polyesters corresponds roughly to the nitrogen content of the resultant polyester, i.e., about 0.5 to 10% by weight, preferably 2 to 6% by weight.
  • a wire insulating lacquer comprising an organic solvent solution of a modified polyester resin of terephthalic acid, isophthalic acid, or mixtures thereof, with a glycol, an alcohol containing more than two hydroxyl groups and hydrazine and a curing agent therefor.
  • wire insulating lacquer of claim 4 wherein said resin contains from 0.5 to 10% by weight of chemically bound nitrogen.
  • the wire insulating lacquer of claim 4 wherein said glycol is ethylene glycol and the alcohol containing more than two hydroxyl groups is selected from the group consisting of glycerin, trimethylol propane, pentaerythritol and mixtures thereof.
  • a process for the preparation of a modified polyester resin which comprises esterifying terephthalic acid, isophthalic acid, or a mixture thereof, with a mixture of a glycol and an alcohol containing more than two hydroxyl groups, adding thereto hydrazine hydrate or an aqueous solution thereof, refluxing the resultant mixture and distilling off the water and then maintaining the resultant roduct at an elevated temperature until the desired degree of polycondensation is attained.
  • a process for the preparation of a modified polyester resin which comprises transesterifying a lower alkyl ester of terephthalic acid, isophthalic acid, or a mixture thereof, with a mixture of a glycol and an alcohol containing more than two hydroxyl groups, adding thereto hydrazine hydrate or an aqueous solution thereof, refluxing the resultant mixture and distilling off the water and then maintaining the resultant product at an elevated temperature until the desired degree of polycondensation is attained.
  • a process for manufacturing a wire containing an insulating lacquer thereon which comprises dipping the bare wire in an organic solvent solution of a modified polyester resin of terephthalic acid, isophthalic acid, or mixtures thereof, with a glycol, an alcohol containing more than two hydroxyl groups and hydrazine and a curing agent therefor, and then baking the wire for a time sufficient to obtain a good adherence between the wire and the lacquer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
US676023A 1966-10-18 1967-10-18 Hydrazine-modified polyester resins useful in insulating lacquers for wires Expired - Lifetime US3476708A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED0051334 1966-10-18

Publications (1)

Publication Number Publication Date
US3476708A true US3476708A (en) 1969-11-04

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Country Status (4)

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US (1) US3476708A (de)
AT (1) AT279768B (de)
DE (1) DE1644778C3 (de)
GB (1) GB1171710A (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2137884C3 (de) * 1971-07-29 1982-01-21 Herberts Gmbh, 5600 Wuppertal Verfahren zur Herstellung von stickstoffhaltigen modifizierten Polyesterharzen und diese enthaltende Einbrennlacke

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3161541A (en) * 1959-04-27 1964-12-15 Gen Electric Synthetic resin and conductors insulated therewith
US3345429A (en) * 1964-08-13 1967-10-03 Westinghouse Electric Corp Blended polyester wire enamels and conductors insulated therewith
US3393180A (en) * 1962-06-15 1968-07-16 Bayer Ag Process for preparing polymers containing co-nh-nh-co-groups

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3161541A (en) * 1959-04-27 1964-12-15 Gen Electric Synthetic resin and conductors insulated therewith
US3393180A (en) * 1962-06-15 1968-07-16 Bayer Ag Process for preparing polymers containing co-nh-nh-co-groups
US3345429A (en) * 1964-08-13 1967-10-03 Westinghouse Electric Corp Blended polyester wire enamels and conductors insulated therewith

Also Published As

Publication number Publication date
DE1644778B2 (de) 1975-02-06
DE1644778C3 (de) 1975-09-11
AT279768B (de) 1970-03-25
DE1644778A1 (de) 1971-07-22
GB1171710A (en) 1969-11-26

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